Molecular size and shape properties of diamondoid molecules occurring in crude oil

Jiménez-Cruz, Federico; García-Gutiérrez, José Luis

doi:10.1016/j.arabjc.2020.09.043

Cited by 8 publications

(6 citation statements)

References 23 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…12,27 Favorable Ada binding may also arise from restricted dissociation kinetics, theorized to result from the steric bulk of adamantane deforming the slightly narrower CB [7] portals. 14,17,28,29 Ultimately, these results support the extension of underlying binding affinity and dynamics for CB [7]−guest motifs to the thermodynamics of cross-linking in supramolecular hydrogels. Specifically, these results indicate not only that Ada hydrogel cross-linking is less dynamic but that this motif is subject to a larger thermodynamic, and specifically entropic, driving force favoring complexation.…”

Section: ■ Introductionsupporting

confidence: 61%

“…Eyring analysis further informs the relative enthalpic and entropic contributions of this energy barrier. Notably, Xyl offered a more favorable enthalpy of CB[7] binding compared to Ada, anticipated due to electrostatic association between the protonated Xyl amines and the electronegative carbonyl portals of CB[7] that stabilize their complexation. − The increased energy barrier for Ada cross-link reorganization instead arises from primarily entropic effects, in which the more hydrophobic adamantanol moiety is expected to have a favorable binding entropy due to hydrating water molecules being released into bulk solvent upon complexation, while the more hydrophilic Xyl pays some entropic penalty during the process of binding CB[7]. , Favorable Ada binding may also arise from restricted dissociation kinetics, theorized to result from the steric bulk of adamantane deforming the slightly narrower CB[7] portals. ,,, Ultimately, these results support the extension of underlying binding affinity and dynamics for CB[7]–guest motifs to the thermodynamics of cross-linking in supramolecular hydrogels. Specifically, these results indicate not only that Ada hydrogel cross-linking is less dynamic but that this motif is subject to a larger thermodynamic, and specifically entropic, driving force favoring complexation.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Macromolecular Solute Transport in Supramolecular Hydrogels Spanning Dynamic to Quasi-Static States

Braegelman

Ollier

et al. 2022

ACS Appl. Bio Mater.

View full text Add to dashboard Cite

Hydrogels prepared from supramolecular cross-linking motifs are appealing for use as biomaterials and drug delivery technologies. The inclusion of macromolecules (e.g., protein therapeutics) in these materials is relevant to many of their intended uses. However, the impact of dynamic network cross-linking on macromolecule diffusion must be better understood. Here, hydrogel networks with identical topology but disparate cross-link dynamics are explored. These materials are prepared from cross-linking with host–guest complexes of the cucurbit[7]uril (CB[7]) macrocycle and two guests of different affinity. Rheology confirms differences in bulk material dynamics arising from differences in cross-link thermodynamics. Fluorescence recovery after photobleaching (FRAP) provides insight into macromolecule diffusion as a function of probe molecular weight and hydrogel network dynamics. Together, both rheology and FRAP enable the estimation of the mean network mesh size, which is then related to the solute hydrodynamic diameters to further understand macromolecule diffusion. Interestingly, the thermodynamics of host–guest cross-linking are correlated with a marked deviation from classical diffusion behavior for higher molecular weight probes, yielding solute aggregation in high-affinity networks. These studies offer insights into fundamental macromolecular transport phenomena as they relate to the association dynamics of supramolecular networks. Translation of these materials from in vitro to in vivo is also assessed by bulk release of an encapsulated macromolecule. Contradictory in vitro to in vivo results with inverse relationships in release between the two hydrogels underscores the caution demanded when translating supramolecular biomaterials into application.

show abstract

Section: ■ Introductionsupporting

confidence: 61%

Section: Resultsmentioning

confidence: 99%

Macromolecular Solute Transport in Supramolecular Hydrogels Spanning Dynamic to Quasi-Static States

Braegelman

Ollier

et al. 2022

ACS Appl. Bio Mater.

View full text Add to dashboard Cite

show abstract

“…For higher-order diamondoids, isomers are distinguished by the physical arrangement of the cages and the number of isomers increases rapidly with size (Oomens et al 2006). Thus, not only does this molecular class possess interesting optical, physical, and chemical properties with applications to medicine and technology, but they have also often been used as models to investigate the dependence of known properties of nanodiamonds based on their size and shape (Landt et al 2009b;Dahl et al 2010;Schreiner et al 2011;Patrick & Giustino 2013;Richter et al 2014;Gali et al 2016;Jiménez-Cruz & García-Gutiérrez 2020).…”

Section: Introductionmentioning

confidence: 99%

Optical Spectrum of the Diamantane Radical Cation

Crandall

Radloff

Förstel

et al. 2022

ApJ

View full text Add to dashboard Cite

Similarities exist between the infrared spectra of diamondoids and unidentified infrared emission bands seen in the spectra of young stars with circumstellar disks. Due to their low ionization energy and absorption in the visible range, the radical cations of these highly stable molecules are also suggested to contribute to the well-known but largely unassigned diffuse interstellar bands. However, thus far only the optical spectrum of the adamantane cation (Ada+) has been measured in the laboratory, which is required for astronomical identification. Herein, we present the optical spectrum of the diamantane radical cation (C14H20 +, Dia+, D 3d) between 400 and 1000 nm in the gas phase. The spectra are obtained by electronic photodissociation (EPD) of mass-selected ions generated by electron ionization and trapping in a cryogenic trap at 5 K. The most intense fragmentation channels are the losses of H and C4H9. The optical spectrum reveals two broad and unresolved bands centered near 760 and 450 nm that are assigned to the D 2(2 E u) ← D 0(2 A 1g) and D 5(2 A 2u) ← D 0(2 A 1g) transitions using density functional theory. Despite a vibrational temperature below 20 K, no vibrational structure is resolved. Franck–Condon simulations of the D 5 ← D 0 transition predict intense vibronic progressions that become indiscernible from the band contour at spectral widths above 350 cm−1. Thus, the lack of resolved spectral features is attributed to lifetime broadening, Franck–Condon congestion arising from geometric changes, and possibly vibronic coupling. In addition to the EPD spectra, we characterize the ground state of Dia+ by analysis of a remeasured photoelectron spectrum and a predicted infrared spectrum.

show abstract

“…7b,d). In this case Ada is probably trapped into the internal super-cages of the framework, due to its large size (6.8 x 7.6 × 7.4 Å) [48], bigger than the 10 MR apertures. It is, however, immediately burned when O 2 was sent in the flow, (see the lower plots of Figs.…”

Section: Tablementioning

confidence: 99%

Insight on Mww Siliceous Zeolites: From 2d Precursors Toward 3d Structure

Rosso,

Airi,

Signorile

et al. 2023

Preprint

View full text Add to dashboard Cite

Molecular size and shape properties of diamondoid molecules occurring in crude oil

Cited by 8 publications

References 23 publications

Macromolecular Solute Transport in Supramolecular Hydrogels Spanning Dynamic to Quasi-Static States

Macromolecular Solute Transport in Supramolecular Hydrogels Spanning Dynamic to Quasi-Static States

Optical Spectrum of the Diamantane Radical Cation

Insight on Mww Siliceous Zeolites: From 2d Precursors Toward 3d Structure

Contact Info

Product

Resources

About